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Title: Artificial hydrogenases based on cobaloximes and heme oxygenase

Journal Article · · ChemPlusChem
 [1];  [1];  [1];  [2];  [3];  [2];  [2];  [3];  [4]; ORCiD logo [1]
  1. Univ. Grenoble Alpes, Grenoble Cedex (France)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Tohoku Univ., Sendai (Japan)
  4. Univ. Grenoble Alpes, Grenoble Cedex (France); Univ. Pierre et Marie Curie, Paris (France)
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Abstract The insertion of cobaloxime catalysts in the heme‐binding pocket of heme oxygenase (HO) yields artificial hydrogenases active for H 2 evolution in neutral aqueous solutions. These novel biohybrids have been purified and characterized by using UV/visible and EPR spectroscopy. These analyses revealed the presence of two distinct binding conformations, thereby providing the cobaloxime with hydrophobic and hydrophilic environments, respectively. Quantum chemical/molecular mechanical docking calculations found open and closed conformations of the binding pocket owing to mobile amino acid residues. HO‐based biohybrids incorporating a {Co(dmgH) 2 } (dmgH 2 =dimethylglyoxime) catalytic center displayed up to threefold increased turnover numbers with respect to the cobaloxime alone or to analogous sperm whale myoglobin adducts. This study thus provides a strong basis for further improvement of such biohybrids, using well‐designed modifications of the second and outer coordination spheres, through site‐directed mutagenesis of the host protein.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1351308
Alternate ID(s):
OSTI ID: 1401439
Journal Information:
ChemPlusChem, Vol. 81, Issue 10; ISSN 2192-6506
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science

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Cited By (2)

Host–guest chemistry between cyclodextrin and a hydrogen evolution catalyst cobaloxime journal January 2019
Supramolecular assembly of cobaloxime on nanoring-coated carbon nanotubes: addressing the stability of the pyridine–cobalt linkage under hydrogen evolution turnover conditions journal January 2016

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
biohybrid species
hydrogen evolution
artificial enzymes
bioinspired chemistry
cobalt
heme proteins
enzyme models
biohybrids